Alkoxy-containing reaction product



Sept. 8, 1959 Filed July 20, 1956 E. J. KAHLER ALKOXY-CONTAINING REACTION PRODUCT O O O O O (NOISSIINSNVH WAVELENGTH, MICRONS 2 Sheets-Sheet l .Z INFRARED ABSORPTION SPECTRUM OF REACTION PRODUCT OF SODIUM METHYLATE WITH P CI NO "l [q INVENTOR.

Ernest J. Kchler BY Mybuau/ p 8, 1959 I E. J. KAHLER 2,903,476

ALKOXY-CONTAINING REACTION PRODUCT INFRARED ABSORPTION SPECTRUM OF REACTION PRODUCT OF SODIUM ETHYLATE 9 m M Z O D g #f m g E w 2 R w j 3 g g B 5)- I R 0 0 2 l0 I Q a?! m E E 5 I F r0 NI l INVENTOR. N Ernest J. Kohler 3 33 8 3 8 0 BY X (NOISSIWSNVHL EIONVLLIINSNVHJ. I W

ATTORNEYS.

ALKOXY-CONTAINING REACTION PRODUCT Ernest J. Kahler, Columbus, Ohio,.assiguor, by mesne assignmentsflo Peunsalt Chemicals Corporation, a cor- ;poration. of Pennsylvania Applicatiou July 20, 1956, Serial No. 599,036

7 Claims. (Cl. 260-4161) This invention'relates to the process of reacting compoundsofthe class P X NO, wherein X is halogemwith an alkali metal alcoholate and the reaction products 'forrned thereby. The said reaction products exhibit insecticidal properties.

The starting compoundsof the'class P X NO, wherein X is halogen, are disclosed and claimed in applicants copending application, Serial No. 565,794, filed February 16, 1956. As disclosed therein, the compound P X NO may be prepared by reacting phosphorus pentahalide with a mineral acid 'saltof hydroxylamine. The halogen of the phosphorus pentahalide, of course, is the halogen desired in the .P X 'NO. Thus, in the production of P Cl NO, phosphorus pentachloride is used. It is preferable to use a hydrogen halide salt of hydroxylaminetbecause the volatile nature of the hydrogen halide permits easy separation of the-hydrogen halide from the resulting reaction mixture. As also set forth in the copending'application, the reaction between the phosphorus pentahalide and :the hydrogen halide salt of hydroxylamine should be stopped at the cessation of evolution of chlorine gas from the reaction mixture for maximum yield of 2 5N0- :"L'he structure of P' X NOL-il1ustrating X as chlorine, has been determined as follows:

a his.

The copending application should be consulted for more detailed information as to the production of the starting compounds P X NO.

Briefly, applicant has discovered that compounds of the class P X NO, wherein X is halogen, react with alkali metal alcoholates to form the halide salt of the alkali metal and yield a major reaction product containing alkoxy groups. The reaction can conveniently be carried out at ordinary room temperature in appropriate solvents for the P X NO and the alkali metal alcoholates. As disclosed in said copending application, appropriate solvents for P X NO include aromatic hydrocarbons, aliphatic hydrocarbons, chlorinated hydrocarbons, and ethers. The ialcoholate may be dissolved in any alkyl alcohol and conveniently the same alcohol of which the alcoholate is a derivative. The following examples are illustrative of the invention.

EXAMPLE I A solution of fresh sodium methylate was prepared in an excess of methanol. The sodium methylate solution was cooled to about 10-15 C. and a benzene solution of P Cl NO was slowly added to the mixture while stirring. The P CI NO was added in a sufiicient amount to neutralize the sodium methylate. The reaction mixture was agitated at room temperature for between 0.5- 1.0 hour. The reaction mixture was then filtered to remove the NaCl. moved under slight vacuum. The product was then col- The benzene-methanol solvent was relected by vacuum distillation at 104-120 C. at 0.3 millimeter of mercury. The collected product boiling within this range had a refractive index of 11 5 1.437.

EXAMPLE 11 Following the same procedure as in Example I, fresh sodium methylate dissolved in excess methanol wasreacted with P Cl NO dissolved in benzene. After the NaCl was filtered 01f, the benzene-methanol solvent was removed under slight vacum. The reaction mixture was then subjected to vacuum distillation and the product boiling from 114 C. under 0.6 millimeter of mercury to C. under 0.45 millimeter of mercury was collected.

EXAMPLE III Fresh sodium methylate dissolved in excess methanol was reacted with a benzene solution of P Cl NO in the same manner as the :previous examples. The benzenernethanol solvent was removed under slight vacuumgafter the NaCl was filtered off. The reaction mixture was subgroups and-only traces of-hydroxy groups, whichbecame less evident upon further purification of the product. A representative infrared spectrum of the alkoxy reaction product formed by the reaction of sodium methylate with 1P Cl NO is shown in Fig. 1. Analysis of the reaction product shows that the percentage relationship between the phosphorus, nitrogen, carbon, and hydrogen content is, respectively, about 22.0 percent, 5.6 percent, 24.2 percent, and 6.0 percent. The molecular weight is determined tobe approximately 244.

The same reaction as described in the above examples has also been applied to P Cl NO and sodium ethylate. This reaction is described in the following examples:

EXAMPLE IV Fresh sodium ethylate dissolved in excess ethanol was cooled to about 10-15 C. and a benzene solution of P Cl NO slowly added during stirring. The P Cl NO was added in an amount sufficient to neutralize the sodium ethylate. The reaction mixture was stirred at room temperature for about 0.5 to 1.0 hour. The reaction mixture was then filtered to remove the NaCl and then subjected to distillation under slight vacuum to remove the benzene-ethanol solvent. The reaction mixture was then subjected to vacuum distillation and the product boiling within the range of 134 C. under 0.5 millimeter of mercury to 140 C. under 2.1 millimeters of mercury was collected.

EXAMPLE V A sodium ethylate solution in ethanol was treated with P Cl NO in the same manner as in Example IV. After removal of the NaCl and the benzene-ethanol solvent the mixture was subjected to vacuum distillation to collect a product boiling within the range of 122 C. to C. under 0.5 millimeter of mercury pressure.

As in the case of the reaction with sodium methylate, slightly more than 1.0 mole of P Cl NO was necessary to neutralize 5 moles of sodium ethylate. The phosphorus, nitrogen, carbon, and hydrogen content of the reaction mixture was analyzed to be approximately 19.8 percent, 4.06 percent, 36.9 percent, and 7.7 percent, respectively. The product had a refractive index within the range of 12 1.4331 to 1.4305. Infrared analyses shows the presence of C H O- groups. An infrared spectrum representative of the alkoxy reaction product of sodium ethylate with P Cl NO is shown in Fig. 2.

These alkoxy reaction products have insecticidal properties, as illustrated in the following example:

EXAMPLE VI The alkoxy reaction product of P Cl NO and sodium ethylate, prepared as described in Example IV, was used as a contact spray on houseflies. A spray solution conmay be made without departing from the invention in its broader aspects. Therefore, the appended claims are intended to cover all such changes and modifications as fall within the true spirit and scope of the invention.

What is claimed is:

1. The process comprising treating P CI NO with an alkali metal alcoholate of a lower alcohol.

2. The process comprising treating P Cl NO with an alkali metal methylate.

3. The process comprising treating P Cl NO with an alkali metal ethylate.

4. The process comprising treating P Cl NO with an alkali metal alcoholate of a lower alcohol whereby alkali metal chloride is formed, separating the resulting alkali taming milligrams 0f the Product P mi11i1it61 9 15 metal chloride from the reaction mixture, and separataceton WES pr y d 011 two 10m 0f houseflles caged 1H ing from the resulting reaction mixture a reaction product containers. The number of flies knocked down were containing lk groups counted at various time intervals. The kill at the end 5 Th lk d t f d b th ti f of 24 hours Was ccfmpared Wlth Obtallled using a P Cl NO and an alkali metal alcoholate of a lower alcof DDT 50111111011 of 3-125 mllhgfams of DDT P hol, said product being separated from the alkali metal milliliter of acetone. Acetone alone was also run as a h lid f med d i id ti control check. The results obtained are shown in the 6 Th lk ti d t f P C1 NO d an summary b low. The alkoxy re i n pro ct of P2 l5N alkali metal methylate having an infrared spectrum corand sodium ethylate is shown equal to DDT as a killing re onding to the spectrum shown in Fig. 1. agent for houseflies. 7. The alkoxy reaction product of P Cl NO and an Summary Percent 0.5 Hour 4.5 Hours 24 Hours Ave. Agent Run Total Knocked Percent Percent No. Flies Down Dead Dead Up Down Up Down Up Down Acetone A 57 3.5 55 2 57 0 65 2 4 5 B 44 16 37 7 42 2 41 3 7 DDT A so 100 0 e0 1 59 1 59 98 99 B 52 100 o 52 2 50 0 52 100 PgClBNO-NQOCzHs reaction product. A 53 100 0 53 0 53 0 53 100 100 In summary, applicant has discovered that compounds of the class P X NO, wherein X is halogen, may be reacted with an alkali metal salt of any alkyl alcohol. This invention represents, so far as is known, the first instance of this type of a reaction to produce an insecticidal reaction product. The product may be applied to the insectinfested area or the area desired to be protected against insects in any conventional manner, such as by spraying, coating, or other methods of applying insecticidal compositions.

While particular embodiments of this invention have been shown and described, it will be obvious to those skilled in the art that various changes and ramifications alkali metal methylate having an infrared spectrum corresponding to the spectrum shown in Fig. 2.

References Cited in the file of this patent Besson et al.: Compt. Rend. 143, 38 (1906). Mellor: Comprehensive Treatise on Inorganic and Theoretical Chemistry, Longmans, Green and Co., N.Y.,

& Sons, N.Y. (1952 

4. THE PROCESS COMPRISING TREATING P2CL5NO WITH AN ALKALI METAL ALCOHOLATE OF A LOWER ALCOHOL WHEREBY ALKALI METAL CHLORIDE IS FORMED, SEPARATING THE RESULTING ALKALI METAL CHLORIDE FROM THE REACTION MIXTURE, AND SEPARATING FROM THE RESULTING REACTION MIXTURE A REACTION PRODUCT CONTAINING ALKOXY GROUPS. 